US7041778B1 - Processable thermally stable addition polyimide for composite applications - Google Patents

Processable thermally stable addition polyimide for composite applications Download PDF

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US7041778B1
US7041778B1 US10849634 US84963404A US7041778B1 US 7041778 B1 US7041778 B1 US 7041778B1 US 10849634 US10849634 US 10849634 US 84963404 A US84963404 A US 84963404A US 7041778 B1 US7041778 B1 US 7041778B1
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resin
invention
polyimide
composite
dianhydride
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David B. Curliss
Jason E. Lincoln
Katie E. Thorp
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US Air Force
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US Air Force
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents

Abstract

A novel polyimide resin consisting essentially of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,2 bis (3′,4′-dicarboxy phenyl) hexafluoro propane dianhydride (6FDA), 2-(3,4-dicarboxyphenyl)-1-phenylacetylene anhydride (4-PEPA) and an aromatic diamine.

Description

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority of the filing date of Provisional Application Ser. No. 60/477,034, filed Jun. 5, 2003.

RIGHTS OF THE GOVERNMENT

The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.

BACKGROUND OF THE INVENTION

The present invention relates to novel polyimide resins.

The cost and weight of aerospace structures can be significantly reduced by the application of high-performance polymeric composites. By replacing metallic components with composite materials, significant weight and cost savings between 25 and 30 percent can be realized. The advent of high modulus fibers and thermally stable polymers made it possible for the introduction of composites into 316° C. (600° F.) temperature regimes. To this end, researchers at NASA Lewis Research Center developed a high-temperature addition polyimide called PMR-15 (Polymerization of Monomeric Reactants, 1500 molecular weight), which, over several decades, became the high-temperature matrix resin “work horse” for the aerospace industry for composite applications in the range of 250° C. to 325° C. The reactant monomers for PMR-15 consist of the monomethyl ester of 5-norbornene 2,3-dicarboxylic acid (nadic ester, NE), the dimethyl ester of 3,3′,4,4′-benzophenonetetracarboxylic acid (BTDE), and 4,4′-methylenedianiline (MDA).

However, PMR-15 contains 4,4′-methylenedianiline (MDA), a known animal carcinogen, a suspected human carcinogen, and a known kidney and liver toxin. When quantities of PMR-15 prepreg are being manufactured, or when this material is being produced into composite structures, exposure to MDA becomes a serious health hazard.

Currently, researchers at NASA-Lewis have developed a polyimide resin called AMB-21 which replaces MDA with 2,2-bis(4-[4-aminopnenoxyl]phenyl)propane (BAPP), a non-toxic, non-carcinogenic monomer. AMB-21 has further benefit in that it may be formed into composite components by using resin transfer molding (RTM). RTM fabrication techniques fall into the category of “low-cost” composite processing, since RTM can cut the manufacturing costs by up to 50%. Unfortunately, AMB-21 has a glass transition temperature (after post-cure) of only 285° C., which also falls short of the PMR-15 goal to achieve a 316° C. composite use-temperature.

Accordingly, it is an object of the present invention to provide a novel polyimide resin which overcomes many of the disadvantages of known polyimide resins.

Other objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided a novel polyimide resin consisting essentially of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,2 bis (3′,4′-dicarboxy phenyl) hexafluoro propane dianhydride (6FDA), 2-(3,4-dicarboxyphenyl)-1-phenylacetylene anhydride (4-PEPA) and an aromatic diamine.

DETAILED DESCRIPTION OF THE INVENTION

The resin of this invention is prepared in a suitable solvent at about 65% to 85% solids concentration, i.e., dianhydride monomers and diamine. By controlling the stoichiometric ratio of monomers (6FDA, BTDA, BPDA, 4-PEPA, and diamine) the average degree of oligomerization is limited to the range of about 2.0 to 8.0.

The polyimide system of the invention may be created in any of a number of different physical forms, as will be appreciated by one of ordinary skill. The monomeric reactant mixture is typically in solution, in which case suitable solvents and co-solvents may be used, as appropriate. For example, any alcohol or combination of alcohols may be used, with methanol being particularly advantageous. Alternatively, as understood by persons of ordinary skill, high-boiling, aprotic solvents may be beneficial when making powders. Non-limiting examples of such solvents include NMP, DMSO, m-cresol, pyridine, THF, DMF, xylene, and diglyme, with NMP being especially beneficial.

The polyimide system of the invention has many uses for the fabrication of high temperature composite components for airframe, turbine engine, missile, rocket and rocket motor applications. The technology is most useful for components that can be most effectively manufactured using a prepreg approach to composite fabrication with autoclave or press molding. The properties of the polyimide system allow thick composite parts to be fabricated at relatively low pressures. The polyimide system is also suitable for numerous automotive and industrial applications that employ prepreg-based composite manufacturing processes.

The following example illustrates the invention:

EXAMPLE

6 moles of 6FDA, 1 mole of BTDA, 1 mole of BPDA and 2 moles of 4-PEPA were added as solids to methanol in an appropriate sized reactor at 60% solids level. This system was stirred and heated to reflux, then refluxed for at least 2 hours to ensure complete conversion of the anhydride mixture to alkyl-esters. 9 moles of a 50% m-PDA and 50% p-PDA mixture was added to the reaction pot and stirred until dissolved.

This resin solution has excellent solution stability and can then be used directly to coat a fabric or fiber reinforcement to make a “prepreg” used to manufacture composites. The resin solution can also be used directly to make a film suitable for prepregging or use an adhesive. When cured for 3 hours at 700° F., this resin solution yields a cured polymer with a glass transition temperature of approximately 370° C., exhibiting low melt viscosity relative to PMR-15. The glass transition temperature and melt viscosity can be tailored by variation of the diamine and dianhydride ratios.

The resin solution can also be further worked up through addition of fillers or by tailoring the solids level, or by adding co-solvent(s) to create a resin useable as an adhesive. The resin solution can also be heated to evaporate solvent and also cause reaction between the monomeric components to make an oligomeric polyimide resin without solvent. Such an imidized oligomeric polyimide resin can also be used to treat fiber reinforcements or it can be directly molded to produce useful articles.

Having thus described exemplary embodiments of the present invention, it should be noted by those skilled in the art that the disclosures herein are exemplary only and that alternatives, adaptations and modifications may be made within the scope of the present invention.

Claims (2)

1. A novel polyimide resin consisting essentially of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,2 bis (3′,4′-dicarboxy phenyl) hexafluoro propane dianhydride (6FDA), 2-(3,4-dicarboxyphenyl)-1-phenylacetylene anhydride (4-PEPA) and an aromatic diamine, wherein the mole ratio of 6FDA:BTDA:BPDA:4-PEPA is 6:1:1:2 and wherein said aromatic diamine is a 1:1 mixture of m-PDA and p-PDA.
2. The resin of claim 1 wherein the average degree of oligomerization is about 2.0 to 8.0.
US10849634 2003-06-05 2004-05-18 Processable thermally stable addition polyimide for composite applications Active US7041778B1 (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1854830A2 (en) * 2006-05-12 2007-11-14 General Electric Company Polyimide blend with tailorable properties
US20070265422A1 (en) * 2006-05-12 2007-11-15 General Electric Company Method for making copolymeric polyimide resins
US20070265417A1 (en) * 2006-05-12 2007-11-15 General Electric Company Crosslinked polyimide copolymer material
US20070265420A1 (en) * 2006-05-12 2007-11-15 General Electric Company fiber reinforced gas turbine engine component
US20070265421A1 (en) * 2006-05-12 2007-11-15 General Electric Company Method for making a prepolymer polyimide resin blend
US20080300374A1 (en) * 2007-05-31 2008-12-04 The Boeing Company Dinadic phenyl amine reactive endcaps
US20080300360A1 (en) * 2007-05-31 2008-12-04 The Boeing Company Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication
US20080319159A1 (en) * 2007-06-22 2008-12-25 The Boeing Company Single-step-processable polyimides
US20090148275A1 (en) * 2007-12-05 2009-06-11 United Technologies Corporation Laminate air seal for a gas turbine engine
EP2083037A3 (en) * 2007-12-27 2010-05-26 General Electric Company RTM and RI Processible Tailorable Polyimide Resin Systems and Composite Articles Formed Therefrom
WO2014007894A2 (en) 2012-04-30 2014-01-09 The Boeing Company Composites including silicon-oxy-carbide layers and methods of making the same

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US4485231A (en) * 1981-07-24 1984-11-27 Hughes Aircraft Company Isoimide containing oligomers
US5138028A (en) * 1990-02-20 1992-08-11 National Starch And Chemical Investment Holding Corporation Polyimides end-capped with diaryl substituted acetylene
US5171828A (en) * 1989-10-26 1992-12-15 Occidental Chemical Corporation Copolyimide ODPA/BPDA/4,4'-ODA or P-PDA
US5175241A (en) * 1989-12-28 1992-12-29 The Dexter Corporation Polyimide with reduced anhydride content
US5196500A (en) * 1990-12-17 1993-03-23 E. I. Du Pont De Nemours And Company Tetrapolyimide film containing benzophenone tetracarboxylic dianhydride
US5412066A (en) 1994-03-03 1995-05-02 Ther United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phenylethynyl terminated imide oligomers
US5426234A (en) 1993-04-02 1995-06-20 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phenylethynyl terminated reactive oligomer
US5567800A (en) 1994-10-28 1996-10-22 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom
US6127509A (en) 1996-12-05 2000-10-03 E. I. Du Pont De Nemours And Company Polyimides having high Tg, high TOS, and low moisture regain

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4485231A (en) * 1981-07-24 1984-11-27 Hughes Aircraft Company Isoimide containing oligomers
US5171828A (en) * 1989-10-26 1992-12-15 Occidental Chemical Corporation Copolyimide ODPA/BPDA/4,4'-ODA or P-PDA
US5175241A (en) * 1989-12-28 1992-12-29 The Dexter Corporation Polyimide with reduced anhydride content
US5138028A (en) * 1990-02-20 1992-08-11 National Starch And Chemical Investment Holding Corporation Polyimides end-capped with diaryl substituted acetylene
US5138028B1 (en) * 1990-02-20 1996-12-24 Nat Starch Chem Invest Polyimides end-capped with diaryl substituted acetylene
US5196500A (en) * 1990-12-17 1993-03-23 E. I. Du Pont De Nemours And Company Tetrapolyimide film containing benzophenone tetracarboxylic dianhydride
US5426234A (en) 1993-04-02 1995-06-20 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phenylethynyl terminated reactive oligomer
US5412066A (en) 1994-03-03 1995-05-02 Ther United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phenylethynyl terminated imide oligomers
US5567800A (en) 1994-10-28 1996-10-22 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom
US5681967A (en) 1994-10-28 1997-10-28 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phenylethynyl phthalic anhydride
US6127509A (en) 1996-12-05 2000-10-03 E. I. Du Pont De Nemours And Company Polyimides having high Tg, high TOS, and low moisture regain

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1854830A3 (en) * 2006-05-12 2007-12-12 General Electric Company Polyimide blend with tailorable properties
US20070265422A1 (en) * 2006-05-12 2007-11-15 General Electric Company Method for making copolymeric polyimide resins
US20070265417A1 (en) * 2006-05-12 2007-11-15 General Electric Company Crosslinked polyimide copolymer material
US20070265420A1 (en) * 2006-05-12 2007-11-15 General Electric Company fiber reinforced gas turbine engine component
US20070265421A1 (en) * 2006-05-12 2007-11-15 General Electric Company Method for making a prepolymer polyimide resin blend
US20070265416A1 (en) * 2006-05-12 2007-11-15 General Electric Company Polyimide blend with tailorable properties
EP1854830A2 (en) * 2006-05-12 2007-11-14 General Electric Company Polyimide blend with tailorable properties
US8309663B2 (en) 2007-05-31 2012-11-13 The Boeing Company Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication
US20080300374A1 (en) * 2007-05-31 2008-12-04 The Boeing Company Dinadic phenyl amine reactive endcaps
US20080300360A1 (en) * 2007-05-31 2008-12-04 The Boeing Company Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication
US20130101742A1 (en) * 2007-05-31 2013-04-25 The Boeing Company Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication
WO2008150677A1 (en) * 2007-05-31 2008-12-11 The Boeing Company Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication
US8808804B2 (en) * 2007-05-31 2014-08-19 The Boeing Company Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication
US7825211B2 (en) 2007-06-22 2010-11-02 The Boeing Company Single-step-processable polyimides
US20080319159A1 (en) * 2007-06-22 2008-12-25 The Boeing Company Single-step-processable polyimides
US8128100B2 (en) 2007-12-05 2012-03-06 United Technologies Corporation Laminate air seal for a gas turbine engine
US20090148275A1 (en) * 2007-12-05 2009-06-11 United Technologies Corporation Laminate air seal for a gas turbine engine
EP2083037A3 (en) * 2007-12-27 2010-05-26 General Electric Company RTM and RI Processible Tailorable Polyimide Resin Systems and Composite Articles Formed Therefrom
WO2014007894A2 (en) 2012-04-30 2014-01-09 The Boeing Company Composites including silicon-oxy-carbide layers and methods of making the same

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